KR19990007829A - Process for preparing ether compound - Google Patents

Abstract

Compound represented by the formula (I),

(A) nickel in an amount corresponding to 10 to 70 weight percent of the metal nickel, and

(B) oxides of silicon, aluminum, magnesium, titanium and zirconium; And reacting at least one of these oxides with hydrogen in the presence of a solid catalyst consisting of at least one compound selected from the group consisting of synthetic or natural inorganic oxides having their structural units, thereby preparing ether compounds of formula (II) or (III) Here's how:

Formula I

(Wherein R ¹ and R ² are each an alkyl group or a cycloalkyl group, which may be the same or different, in many repeat units R ¹ may be the same or different and n is an integer from 1 to 50)

Formula II

Formula III

Wherein R ¹ , R ² and n are each as defined in formula (I) above)

Description

Process for preparing ether compound

As a method of preparing ethers from acetals, for example, a method of using a combination of an acid and an alkali metal hydrate, a method of using a silicon reagent, and a method of using diborane are described in Experimental Chemistry Lecture 20 (4th edition, Maruzen). (Published by). However, these methods are not preferred as industrial methods because expensive reagents such as alkali metal hydrates, silicon reagents, diborane and the like must be used as stoichiometric amounts of reagents for hydrocracking, and production costs are high.

Ethers may also be prepared from acetals by catalytic hydrocracking in the presence of an acid catalyst. WL Howard et al. Reported that the catalyst can be catalytically hydrocracked to synthesize ethers using rhodium-supported catalysts on alumina in the presence of hydrochloric acid [J. Org. Chem., 26 , 1026 (1961).

In Japanese Patent Laid-Open No. 54 (1979) -135714, an acetal or ketal compound is supported on (1) a halide (aluminum trichloride or boron trifluoride) of a group IIIA element of the periodic table, and (2) platinum or rhodium on a support. A method of preparing an ether by catalytic hydrocracking in the presence of a catalyst is disclosed.

Furthermore, Japanese Patent Laid-Open No. 58 (1983) -189129 discloses a method for producing glycol ether by hydrocracking 1,2-alkyl-1,3-dioxolane in the presence of an ester of palladium and phosphoric acid or phosphoric acid. Is disclosed.

However, since these methods use acidic promoters such as hydrochloric acid, aluminum trichloride, boron trifluoride, phosphoric acid, and the like, corrosion of the device becomes a problem when using a reaction apparatus composed of a conventional material. There is also a need for a complex process of removing the promoter from the product. Therefore, these methods are not useful.

Processes for preparing ethers from acetals by hydrocracking without acid catalysts are also known. Digestion No. 51 (1976) -36106 discloses a process for preparing dialkyl glycol ethers by hydrocracking the foam of glycol ethers in the presence of nickel, cobalt or copper.

Japanese Patent Laid-Open No. 56 (1981) -71031 discloses a process for producing dialkyl glycol ethers by hydrocracking acetal in the presence of a catalyst comprising nickel, molybdenum, and / or rhenium.

M. Verzele et al., J. Chem. Soc., 5598 (1963), ethers are prepared by hydrocracking acetal in the presence of a nickel-kieselguhr catalyst. However, this method involves the hydrocracking of low molecular weight acetals.

In the above-described methods, a low molecular weight compound is used as the target compound. A method for producing a vinyl ether polymer having a terminal ether group by hydrocracking the vinyl ether having a terminal acetal group is not disclosed in any of the above documents.

A process for producing a vinyl ether polymer having terminal ether groups by hydrocracking the vinyl ether polymer having terminal acetal groups is disclosed in US Pat. No. 25,905,98. The purpose of this method is to hydrocrack the polyoxyacetals represented by the following formula (IV) under a pressure of 1000 lb / in ² (68 kg / cm 2) and a temperature of 160 ° C. under neutral or basic conditions in the presence of a metal catalyst for hydrogenation. To prepare an ether compound represented by the formula (V):

(Wherein R ′ and R each represent a hydrocarbon group selected from an alkyl group, an aryl group, and an aralkyl group, m represents an integer of 0 to 10)

Wherein R ', R and m are as described above

In the specification of this patent, the catalyst is specified only as a metal catalyst for hydrogenation. Only Raney nickel was used in the examples. The yield of the product was low as 52%.

International Patent Publication No. WO 93/24435 and Japanese Patent Application Laid-open No. Hei 6 (1994) -128184 disclose the preparation of ether compounds by hydrogenation of acetals or ketals in the presence of a combination of a solid hydrogenation catalyst and a solid acid catalyst. It is. However, because a combination of a solid hydrogenation catalyst and a solid acid catalyst is used, when moisture is not completely removed from the reaction system due to the action of the solid acid catalyst, secondary reactions such as hydrolysis of terminal acetal groups in the raw material occur and are caused by hydrogenation. By-products such as alcohols are formed. Therefore, the amount of moisture contained in the raw materials and the catalyst component should be strictly limited. In addition, the industrial application of this method involves the mixing of two types of catalyst components, which requires a process for the separation and recovery of complex catalysts. Yield of the reactants is also not satisfactory.

As mentioned above, an industrially superior method of producing a vinyl ether polymer having terminal ether groups by hydrocracking the vinyl ether polymer having terminal acetal groups has not yet been proposed.

Therefore, it is industrially important to provide a process for producing vinyl ether polymers having terminal ether groups by hydrocracking the vinyl ether polymers having terminal acetal groups without exhibiting sufficient reactivity and good selectivity and causing corrosion of the apparatus used in the reaction. Do.

It is generally known that reactions such as hydrocracking do not proceed easily with high molecular weight compounds. Moreover, the said matter can also apply to the compound represented by General formula (I) which is an objective compound of this invention mentioned later. Compared to low molecular weight aliphatic acetals, it is difficult to complete hydrocracking of the compound represented by the formula (I) under ordinary conditions. When the ether compound obtained by hydrocracking an acetal compound is used in various applications with unreacted material remaining, the expected physical properties are often not shown. For example, viscosity, adhesiveness, strength, electrical properties, and thermal stability tend to be different from expected physical properties. In addition, these properties tend to change over time and significantly deteriorate in stability during use. This tendency is believed to occur due to changes in the acetal moiety of the unreacted terminus under different use conditions. It is well known that acetals are converted to aldehydes, alcohols, acids, unsaturated ethers and the like under various conditions.

In order to completely hydrocrack the less reactive polymeric material, it is generally necessary to carry out the reaction under stringent conditions by adjusting the reaction conditions such as temperature and pressure. However, since the compound represented by the formula (I) used as a raw material has many alkoxy groups in the molecule, it is necessary to prevent strict conditions causing side reactions such as desorption of other alkoxy groups and isomerization of the structure as well as the acetal structure. .

Accordingly, two methods for preparing the desired ether compound by 1) converting a low reactivity high molecular weight acetal compound into an ether compound in a good yield, and 2) inhibiting the production of by-products, to solve the problems described above It is important.

Disclosure of the Invention

It is therefore an object of the present invention to provide a process for producing vinyl ether polymers having terminal ether groups by hydrocracking the vinyl ether polymers having terminal acetal groups, exhibiting sufficient reactivity and good selectivity and without corroding the device used for the reaction. .

As a result of the present inventors' research on the subject, it was found that the above object can be achieved by hydrocracking an acetal compound with hydrogen in the presence of a catalyst containing nickel and a specific inorganic oxide. The present invention has been completed based on the above matters.

The present invention is an acetal compound represented by formula (I),

(A) nickel in an amount corresponding to 10 to 70 weight percent of the metal nickel, and

(B) oxides of silicon, aluminum, magnesium, titanium and zirconium; And reacting at least one of these oxides with hydrogen in the presence of a solid catalyst consisting of at least one compound selected from the group consisting of synthetic or natural inorganic oxides having their structural units, thereby preparing ether compounds of formula (II) or (III) Provides a way to:

(Wherein R ¹ and R ² are each an alkyl group or a cycloalkyl group, which may be the same or different, in many repeat units R ¹ may be the same or different and n is an integer from 1 to 50)

Wherein R ¹ , R ² and n are each as defined in formula (I) above)

The present invention relates to a vinyl ether polymer having a terminal ether group while exhibiting good yield without causing corrosion of the device used for the reaction by hydrocracking the vinyl ether polymer having a terminal acetal group in the presence of a catalyst containing nickel and a specific inorganic oxide. To a method for producing.

The ether compound produced by the method of the present invention is usefully used in solvents, adhesives, resins, organic intermediates, lubricants, insulating oils and surfactants.

Hereinafter, the present invention will be described in more detail. The compound represented by formula (I) is hereinafter referred to as compound (I). The compounds represented by the formulas (II) and (III) are also referred to as compound (II) and compound (III), respectively.

Catalysts used in the present invention include nickel and oxides such as silicon, aluminum, magnesium, titanium and zirconium; And at least one of synthetic or natural inorganic oxides containing at least one of the above oxides as its structural unit. The catalyst contains nickel in an amount corresponding to 10 to 70% by weight of the metal catalyst. As the oxide, silica, alumina, magnesia, titania or zirconia are preferably used. As synthetic or natural organic oxides containing at least one of the above oxides as their structural units, silica-alumina, silica-magnesia, zeolites, activated clay or diatomaceous earth are preferably used. Specific examples of the solid catalysts preferably used in the present invention include nickel-silica-alumina catalysts, nickel-alumina catalysts, nickel-silica-alumina-magnesia catalysts, nickel-zirconia catalysts and nickel-diatomaceous earth catalysts. The solid catalyst may be used alone or in combination of two or more types.

In the present invention, nickel and oxide can be simply mixed and used as a catalyst. However, the catalyst may be preferably used by supporting nickel on the oxide, or by mixing the nickel and the oxide well by a method such as kneading or the like, and then forming the resulting mixture into a solid state. In particular, in order to achieve the object of the present invention, it is important that the two components of the catalyst are present in the same catalyst in the solid phase and always in close proximity to each other during the reaction. The nickel component of the catalyst may be present in the catalyst as a metal state or as an oxide state. It is necessary to contain the nickel component in an amount corresponding to 10 to 70% by weight, preferably 15 to 65% by weight of the metal nickel in order to increase the yield of the reactants and reduce the formation of byproducts. If the content of nickel in the catalyst is larger than the above range, the terminal acetal groups cannot be completely hydrocracked in the molecules of the raw material, and the amount of by-products increases. If the nickel content in the catalyst is less than the above range, hydrocracking of acetal is incomplete. The by-products formed above are considered to be compounds formed by partial cleavage of the long chain methylene chain, compounds from which alkoxy groups other than the acetal structure are released, and compounds formed by sequentially reacting these reactions.

The method for producing the solid catalyst used in the present invention is not particularly limited. Catalysts containing nickel and oxides can be prepared according to various methods such as support, co-precipitation, ion exchange, synthesis in solid phase and kneading. If the requirements disclosed in the present invention are met, commercially available catalysts may be used without further treatment.

As an example of the method for producing the catalyst, a precipitate is formed by neutralizing an aqueous solution of a compound which decomposes by reduction to form metal nickel, such as nickel nitrate, nickel formate and basic nickel carbonate. The precipitate formed is kneaded with a support selected from oxides such as silica, silica-alumina, alumina, magnesia, titania and zirconia and the mixture is dried. The dried mixture is shaped and treated in a reducing atmosphere to obtain a catalyst. In another example of the method, the nickel salt used as the raw material as described above is dissolved in a solvent such as water and then supported on a support selected from the above-described oxide according to a conventional process. The supported material thus prepared is dried and reduced to give a catalyst.

Preferred examples of the alkyl group represented by R ¹ and R ² in formula (I), (II) or (III) respectively include linear or branched alkyl groups having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, Isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group and isooctyl group. Preferred examples of the cycloalkyl group represented by R ¹ and R ² in the formula (I), (II) or (III) include cycloalkyl groups having 3 to 8 carbon atoms, for example cyclopropyl group, cyclobutyl, cyclopen And a cyclo group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

In the preparation of the compound (I) used as a raw material, there is a method obtained by polymerizing an alkyl vinyl ether represented by the following formula (VI) in the presence of acetal represented by the following formula (VII), but also other conventional It may be produced by a method.

CH ₂ = CHOR ¹

CH ₃ CH (OR ² ) ₂

Wherein R ¹ and R ² are the same as described above)

In general, in preparing high molecular weight polymers, polymers having a constant molecular weight are difficult to obtain. Instead, a mixture of polymers having a range of molecular weight distributions is generally obtained. The raw material compound (I) in the present invention may comprise the above mixture of polymers. Compound (I) used as a raw material in the present invention also includes a compound obtained by copolymerizing two or more kinds of vinyl ethers in which R ¹ is different.

Hydrocracking in the process of the invention can be carried out according to the same method as a conventional hydrocracking process. Hydrocracking can be carried out either continuously or batchwise. The catalyst can be used according to the suspended bed mode or the fixed bed mode. A method of recovering the ether compound (III) produced by the reaction by continuously supplying the compound (I) used as a raw material with hydrogen to the reactor filled with the catalyst to proceed with the reaction, that is, according to the fixed bed method The reaction is preferred because the formation of isomers is reduced and the selectivity is increased.

The hydrocracking reaction can also be carried out effectively in a suspended phase manner, ie in the presence of a solid catalyst in suspended conditions.

Reaction temperatures selected in the range of 70 to 200 ° C., preferably 90 to 190 ° C., are preferred to further enhance the effects of the present invention. When the reaction temperature is lower than the above range, the desired hydrocracking reaction does not proceed sufficiently. If the temperature is high compared to the above range, the by-products described above increase. The reaction is carried out under a pressure of 3 to 80 kg / cm 2 G, preferably 3 to 60 kg / cm 2 G.

If the reaction is carried out batchwise, other reaction conditions can be determined as appropriate. The amount and reaction time of the catalyst can be set such that all raw materials are consumed at the selected pressure and selected temperature. The concentration of the catalyst may be 0.01% to 20% by weight, preferably 0.1 to 15% by weight based on the raw material.

The catalyst recovered from the reaction product can be reused by filtration or decantation.

When the reaction is carried out in a continuous manner such as a fixed bed mode, the LHSV [dose-based liquid space velocity of compound (I) used as raw material; (Defined as raw material feed rate, ml / hr) / (quantity of catalyst, ml)] is in the range of 0.01 to 10 hr ⁻¹ , preferably 0.05 to 5 hr ⁻¹ , and GHSV [volume reference gas space velocity of hydrogen gas] ; In the range of (hydrogen gas fed speed, ㎖ / hr) / (amount of catalyst, ㎖)] is 5 to 1000hr ^-1, preferably from 10 to 500hr ^-1. The molar ratio of hydrogen gas and compound (I) is 2 to 3000, preferably 10 to 1000.

In the process of the invention, compound (I) used as raw material can be used for the direct reaction. However, when compound (I) is high molecular weight, it is preferable to dilute compound (I) with a suitable solvent and to use it by decreasing a viscosity. Examples of solvents used for dilution include alcohols such as methanol and ethanol, ethers such as glycol ether, tetrahydrofuran and dioxane, linear or branched aliphatic such as hexane, heptane, octane, nonane, benzene, toluene and xylene or Aromatic hydrocarbons. Aliphatic hydrocarbons are preferably used.

Compounds (II) and (III), which are the target compounds of the process of the present invention, are separated from the reaction product described above by filtration or pouring and then isolated via essential treatments such as distillation, extraction, washing and drying. Can be.

The number of repeat units (ie degree of polymerization) in the ether compounds (II) and (III) obtained according to the process of the present invention may be appropriately selected depending on the desired kinematic viscosity. The repeating unit number is generally selected such that the kinematic viscosity at 40 ° C. is preferably 5 to 1000 cSt, more preferably 7 to 300 cSt. The average molecular weight of compound (II) and compound (III) is generally 150 to 2,000. In addition, compound (II) or compound (III) having a kinematic viscosity outside the above-mentioned range can be used in combination with other compounds having a suitable kinematic viscosity such that the kinematic viscosity of the resulting mixture is adjusted to a value within the above-mentioned range.

According to the present invention, vinyl ether polymers having terminal ether groups can be used to produce vinyl ether polymers having terminal acetal groups in the presence of a catalyst comprising nickel and certain inorganic oxides without causing problems such as corrosion of the apparatus used for the reaction in good yield. It can be prepared by hydrocracking.

The invention will be explained in more detail by the following examples, comparative examples and reference examples.

Reference Example 1 Preparation and Analysis of Catalyst

(1) Nickel-silica-alumina catalyst (catalyst-1)

A solution prepared by dissolving 500 g of ammonium bicarbonate ((NH ₄ ) HCO ₃ ) in 2000 ml of ion-exchanged water in an aqueous solution containing 600 g of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O) under vigorous stirring The solution was neutralized by addition. The resulting solution was left to stand until the precipitate formed subsided. The precipitate was filtered off, washed and the cake obtained was separated and dried.

To the obtained 170 g of cake, 5 g of silica-alumina (alumina, 13%), manufactured by Ilhui Chemical Co., was added as a support. The components were thoroughly kneaded with 50 ml of ion-exchanged water by kneader. The resulting mixture was dried and molded into 4 mm x 3 mm pellets. The obtained pellet was reduced by hydrogen to a maximum temperature of 400 ° C. in a glass reaction tube. After the reaction was completed, the reaction tube was replaced with nitrogen and cooled to room temperature. Air was then slowly introduced into the reaction tube to stabilize the product by oxidation. At this time, the amount of air was adjusted so that the maximum temperature did not exceed 50 ° C. The nickel content in the stabilized nickel-silica-alumina catalyst was about 49% by weight.

(2) Nickel-alumina catalyst (catalyst-2)

280 g of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O) and 120 g of aluminum nitrate (Al (NO ₃ ) ₃ 9H ₂ O) were dissolved in pure water to prepare 640 ml of a solution. Another dilute solution of 750 ml was prepared by diluting 320 g of 25% aqueous NaOH solution with pure water. 200 ml of pure water, which were previously heated to 60 ° C., were added dropwise into a vessel equipped with a stirrer to obtain a neutralized solution. The temperature of the components in the vessel was controlled such that the maximum temperature was maintained at 70 ° C or lower. After the addition of both solutions was terminated, the resulting product was aged. The cake formed was separated by filtration and washed with pure water until no nitrate ions were detected. The wet cake (600-700 mL) obtained was dried at 110 ° C. under an initial nitrogen stream. Then, the temperature was increased to 350 ° C. and the dried cake was decomposed at this temperature for 5-8 hours. To the powder of the catalyst obtained (about 110 g), 2% graphite was added and the mixture was molded into pellets of 4 mm x 3 mm. The obtained pellet was placed in a glass reaction tube. The temperature of the reaction tube was slowly increased to the highest temperature of 400 ° C. The pellet was reduced to hydrogen at this temperature. After the reduction was completed, the reaction tube was replaced with nitrogen and cooled to room temperature. Air was then slowly introduced into the glass tube to stabilize the product by oxidation. The amount of air was controlled so that the maximum temperature did not exceed 50 ° C. The stabilized nickel-aluminum catalyst contained about 44% nickel by weight and its specific surface area was 180 m ² / g.

(3) Nickel-silica-alumina-magnesia catalyst (commercial catalyst) (catalyst-3)

yen. this. Nickel-silica-alumina catalysts produced in Chemcat Company and injection molded to 3/64 in were used. Elemental analysis of the catalyst revealed that the catalyst contained 57 weight percent nickel, 0.5 weight percent aluminum, 6.5 weight percent silicon and 0.04 weight percent magnesium. It was also confirmed that aluminum and silicon were present in the form of oxides. The specific surface area of the catalyst was 230 m ² / g.

(4) Nickel-zirconia catalyst (catalyst-4)

60 g of nickel nitrate (Ni (NO ₃ ) ₂ 6H ₂ O) was dissolved in 50 ml of pure water. The obtained solution was divided into two portions, and then continuously absorbed into 80 g of a zirconia catalyst (3 mm x 3 mm molded product) manufactured by Strem. The product was dried on a rotary evaporator and then placed in a glass reaction tube. The product in the reaction tube was slowly heated under a nitrogen stream and finally calcined at 350 ° C. for 7 hours. After cooling the reaction tube, the nitrogen stream was replaced with a hydrogen stream diluted with nitrogen. Preliminary reduction was carried out at 400 ° C. under the above air stream. The reaction tube was replaced with nitrogen and cooled to room temperature. Next, air was slowly introduced into the reaction tube to stabilize the product by oxidation. The amount of air was controlled so that the maximum temperature did not exceed 50 ° C. The stabilized nickel-zirconia catalyst contained about 17 weight percent nickel, with a specific surface area of 80 m ² / g.

(5) Nickel-silica-alumina catalyst (commercial catalyst) (catalyst-5)

A molded article of a nickel-silica-alumina catalyst manufactured by Ilhui Chemical Co., Ltd. was used. Elemental analysis of the catalyst contained 52 weight percent nickel, 9 weight percent alumina and 16 weight percent silica.

Reference Example 2 (Preparation of Ethyl Vinyl Ether Polymer Having Terminal Acetal Group)

A 5 L glass flask equipped with a dropping funnel, a cooler and a stirrer was charged with 1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 5.0 g of boron trifluoride diethyl etherate. 2500 g of ethyl vinyl ether was added to the dropping funnel and dropped into the flask within 2 hours 30 minutes. During this time, the reaction started, and the temperature of the reaction solution increased. Cooled with an ice water bath and maintained at about 25 ° C. After the dropping was finished, the reaction solution was stirred for an additional 5 minutes. The reaction mixture was then transferred to a wash bath, washed three times with 1000 ml of 5% aqueous sodium hydroxide solution and then three times with 1000 ml of water. The solvent and unreacted raw material were removed under reduced pressure to yield 2833 g of product. ¹ H-NMR analysis was performed to show that the main component of the product was Compound (I), wherein R ¹ and R ² are both ethyl groups. Analysis by gas chromatography and gel chromatography confirmed the product was a mixture of compounds with n from 1 to 20. The kinematic viscosity of the product yielded a kinematic viscosity of 5.18 cSt at 100 ° C. and 38.12 cSt at 40 ° C. when measured by a Cannon-Fenske viscometer.

Reference Example 3 (Preparation of Vinyl Ether Copolymer Having Terminal Acetal Group)

A 5 L glass flask equipped with a dropping funnel, a cooler and a stirrer was charged with 1000 g of toluene, 500 g of acetaldehyde diethyl acetal and 4.5 g of boron trifluoride diethyl etherate. 1600 g of ethyl vinyl ether and 2200 g of isobutyl vinyl ether were placed in a dropping funnel and dropped into the flask within 4 hours. The reaction was initiated and the temperature of the reaction solution increased. Cooling with an ice-water bath maintained the temperature of the reaction solution at about 25 ° C. After the dropping was finished, the reaction solution was stirred for an additional 5 minutes. The reaction mixture was then transferred to a wash bath, washed three times with 1000 ml of 5% aqueous sodium hydroxide solution and then three times with 1000 ml of water. The solvent and unreacted raw material were removed under reduced pressure to yield 3960 g of product. ¹ H-NMR analysis showed that the main component of the product was compound (I), in which R ¹ is a mixture of ethyl and isobutyl groups in the other repeating units, R ¹ and R ² are both ethyl groups at the ends, It was confirmed as a mixture of compounds having. The kinematic viscosity of the product was 112.5 cSt at 40 ° C.

Example 1 Hydrocracking of Vinyl Ether Polymer Having Terminal Acetal Group

The vinyl ether polymer having terminal acetal groups prepared in Reference Example 2 was diluted with the same volume of n-hexane, and the obtained solution was used as a raw material for hydrocracking. A 25 mm inner pressure resistant reaction tube with an outer jacket made of SUS-316 was used as the reactor. The reaction temperature was controlled by passing the heated silicone oil through the jacket.

The nickel-silica-alumina catalyst (catalyst-1) prepared in Reference Example 1 was charged into the reactor. The reaction was carried out at a reaction pressure of 20 kg / cm 2 G and a reaction temperature of 140 ° C. The flow rate of ethyl vinyl ether oligomer diluted with n-hexane was 30 ml / hr (LHSV = 0.3hr- ¹ including n-hexane), and the flow rate of hydrogen gas was 12 normal L / hr (GHSV = 120hr- ¹ ). It was.

The reaction product was collected and n-hexane used as the solvent and ethanol formed by the reaction were removed under vacuum. ¹ H-NMR analysis showed that the product was either compound (II) or compound (III) in which both R ¹ and R ² were ethyl groups (product (A)). The reaction rate of the product was 100% and the selectivity of the product (A) was 92%. The reaction rate was obtained by ¹ H-NMR analysis of the sample prepared at a constant concentration. In the analysis, the integrated value of acetal methine proton (4.8 ppm) was expanded to 1000 times, and the raw material value was integrated at 100%. Although the selectivity is not isomerized by hydrogenation but the ratio which preserve | saved the structure of the product (A) was shown, it integrated by the gas chromatography chart. The product had a kinematic viscosity of 27.6 cSt at 40 ° C.

Examples 2-6 and Comparative Examples 1-3 (reaction using catalysts with different nickel concentrations)

Nickel-silica-alumina catalysts having different nickel concentrations were prepared according to the same procedure as used for preparing Catalyst 1 in Reference Example 1. Hydrocracking reactions were carried out using these catalysts under the conditions shown in Table 1.

Into the reactor used in Example 1, 100 ml of a catalyst containing 4%, 16%, 28%, and 49% nickel was added. The vinyl ether polymer having a terminal acetal group prepared in Reference Example 2 (viscosity 42.2 cSt) was diluted with the same volume of isooctane, and the obtained solution was flown at 30 ml / hr (LHSV = 0.3 hr ^-1 containing isooctane). Fed to the catalyst bed. The flow rate of the hydrogen gas was 12 normal liter / hr (GHSV = 120hr- ¹ ).

The reaction was carried out at various temperatures and under different pressures. Reaction rate and selectivity were obtained in the same manner as in Example 1. The results of the reaction are shown in Table 1.

Nickel content (% by weight) Reaction temperature (℃) Reaction pressure (㎏ / ㎠) % Of reaction % Selectivity Kinematic viscosity (cSt) Example 2 16 140 20 94 91 35.3 Example 3 16 180 25 99 85 33.8 Example 4 28 130 20 95 93 34.5 Example 5 28 150 20 100 91 32.2 Example 6 49 150 7 100 89 32.2 Comparative Example 1 4 150 20 63 45 40.1 Comparative Example 2 4 150 40 70 72 39.4 Comparative Example 3 4 180 20 85 64 38.1

Examples 7-19 (Reactions with Various Types of Catalysts)

One of the catalysts prepared in Reference Example 1 (catalyst-2 to catalyst-5) was charged into the reactor used in Example 1 in the amounts shown in Table 2. The conditions of the catalyst were set to the predetermined conditions shown in Table 2. The ethyl vinyl ether polymer prepared in Reference Example 2 having a terminal acetyl group was diluted with the same volume of isooctane, and a predetermined amount of the obtained solution was fed to the catalyst layer with hydrogen.

Reaction rate and selectivity were obtained by the same method as in Example 1. The results of the reaction are shown in Table 2.

catalyst Reaction temperature (℃) Reaction pressure (㎏ / ㎠) SV of raw material (hr ^-1 ) SV of hydrogen (hr ^-1 ) % Of reaction % Selectivity Example 7 2 140 7 0.3 120 98 92 Example 8 2 160 20 0.3 120 100 85 Example 9 2 150 7 0.6 120 99 89 Example 10 2 140 20 0.3 120 100 82 Example 11 3 120 20 0.3 120 89 88 Example 12 3 160 20 0.6 120 95 86 Example 13 4 150 20 0.3 120 91 77 Example 14 4 150 40 0.2 90 98 79 Example 15 4 170 20 0.2 90 100 73 Example 16 5 140 3 0.6 120 96 70 Example 17 5 140 5 0.6 120 97 82 Example 18 5 140 8 1.0 120 91 83 Example 19 5 140 20 0.8 120 94 90 SV of raw material (hr ^-1 ) = feed amount of raw material (including solvent) (ml / hr) / amount of catalyst (ml) hydrogen of SV (hr ^-1 ) = amount of hydrogen supply (ml / hr) / amount of catalyst ( Ml / hr)

Comparative Example 4 (Reaction with Ruthenium Catalyst)

yen. this. 50 ml of 2% ruthenium / carbon catalyst made by Chemcat Company and 50 ml of silica-alumina [Tomix AD700; Silica: alumina = 10: 1] were mixed with each other and the resulting mixture was charged into a reactor used in Example 1.

The ethyl vinyl ether polymer prepared in Reference Example 2 having terminal acetal groups under a reaction pressure of 20 kg / cm 2 was diluted with the same volume of n-hexane, and the resulting solution with hydrogen at a rate of 30 ml / hr (including solvent LHSV = 0.3 hr ^-1 ) to feed the catalyst bed. The flow rate of the hydrogen gas was 12 normal L / hr (GHSV = 120hr- ¹ ). The reaction rate was 16% when the reaction was carried out at a temperature of 130 ℃, 57% when the reaction was carried out at 180 ℃. In both cases, the selectivity of the ether compound as the target compound was 0%.

Example 20 Hydrocracking of Vinyl Ether Copolymer Having Terminal Acetal Group

In the reactor used in Example 1, 100 ml of nickel-silica-alumina-magnesia catalyst (catalyst-3) prepared in Reference Example 1 was charged. The ethyl vinyl ether polymer prepared in Reference Example 3 having a terminal acetal group was diluted with an equal volume of isooctane at a reaction temperature of 160 ° C. under a reaction pressure of 7 kg / cm 2, and the resulting solution was mixed with hydrogen at a rate of 30 ml / hr. (LHSV = 0.3 hr ^-1 including solvent) was supplied to the catalyst bed. The flow rate of the hydrogen gas was 8 normal L / hr (GHSV = 80hr ⁻¹ ).

After distilling off the solvent, the reaction product was analyzed by ¹ H-NMR. The reaction rate was 100% and the kinematic viscosity of the product was 68.2 cSt at 40 ° C.

Example 21 (hydrocracking by batch reaction)

A 300 g vinyl ether copolymer prepared in Reference Example 3 having 9.0 g of nickel-diatomaceous earth catalyst (N113 manufactured by Ilhui Chemical Co., Ltd.) and terminal acetal groups was charged into a 1 L autoclave made of SUS-316L. The interior of the autoclave was replaced with hydrogen and the hydrogen pressure increased to 35 kg / cm 2 G. The temperature of the autoclave was increased to 140 ° C. and the reaction proceeded at this temperature for 2 hours. A decrease in pressure was observed by the reaction while the temperature increased and the reaction proceeded, and the reaction pressure was sometimes maintained at 35 kg / cm 2 G by the additional introduction of hydrogen.

The catalyst was removed from the reaction product by filtration and the volatile components were removed by distillation. The resulting reaction product was analyzed by ¹ H-NMR and the reaction rate was 100%. The yield of the reaction product was 271.5 g (90.5 weight% based on vinyl ether copolymer with terminal acetal groups used as raw material). Kinematic viscosity was 88.3 cSt at 40 ℃.

Example 22

300 g of vinyl prepared in Reference Example 3 having 9.0 g of nickel-diatomaceous earth catalyst ((N. E. Chemcat Company; 57 wt% supported nickel content) and terminal acetal groups in a 1 L autoclave consisting of SUS-316L The ether copolymer was charged in. The autoclave was replaced with hydrogen and the hydrogen pressure was increased to 35 kg / cm 2 G. The temperature of the autoclave was increased to 140 ° C. and the reaction proceeded at this temperature for 2 hours. A decrease in pressure was observed by the reaction while the temperature increased and the reaction proceeded, and the reaction pressure was sometimes maintained at 35 kg / cm 2 G by the additional introduction of hydrogen.

The catalyst was removed from the reaction product by filtration and the hard powder was distilled off. The resulting reaction product was analyzed by ¹ H-NMR and the reaction rate was 100%. The recovery of the reaction product was 270.0 g (90.0% by weight relative to the vinyl ether copolymer having terminal acetal groups used as raw material). The kinematic viscosity was 89.0 cSt at 40 ° C.

Comparative Example 5

(1) 100 g of Raney nickel (manufactured by Natural Fine Chemicals Co., Ltd .; M300T) (functional state) were placed in a flask. The supernatant was removed and 200 g of absolute ethanol was added to the remaining catalyst. The mixture was stirred well and left to stand. Supernatant was removed. 200 g of absolute ethanol was added again to the remaining catalyst and the mixture was well stirred. The operation was repeated five times.

(2) 30 g of zeolite (manufactured by Tosoh Corporation; HSZ330HUA) was dried at a temperature of 150 ° C. in a vacuum oven for 1 hour. After drying, a vacuum vacuum pump was used to reduce the pressure in the vacuum oven.

(3) 9 g Raney nickel prepared and developed in (1) above in a 1 L autoclave made of SUS-316L, 200 g hexane, 9 g zeolite obtained in (2) above, and 15 g acetaldehyde diethylacetal Was added. The autoclave was replaced with hydrogen. The temperature was increased to 130 ° C. within 30 minutes with stirring. The reaction was run at 130 ° C. for an additional 30 minutes. After the reaction was completed, the reaction product was cooled to room temperature and then the pressure was relaxed to atmospheric pressure. The reaction product was left to stand for 30 minutes to allow the catalyst to precipitate, and the reaction solution was poured off and removed.

(4) 300 g of vinyl ether copolymer prepared in Reference Example 3 having 9.0 g of Raney nickel and terminal acetal groups developed in a 1 L autoclave made of SUS-316L was charged. The interior of the autoclave was replaced with hydrogen and the hydrogen pressure increased to 35 kg / cm 2 G. Under stirring the temperature of the autoclave was increased to 140 ° C. and reacted at this temperature for 2 hours. A decrease in pressure was observed by the reaction while the temperature increased and the reaction proceeded, and the reaction pressure was sometimes maintained at 35 kg / cm 2 G by the additional introduction of hydrogen.

The catalyst was filtered off, the hard component was distilled off, and the resulting reaction product was analyzed by ¹ H-NMR. As a result, the reaction rate was 100%. The recovery of the reaction product was 247.2 g (82.4% by weight relative to the vinyl ether copolymer having terminal acetal groups used as raw material). The kinematic viscosity was 90.2 cSt at 40 ° C.

Ether compounds prepared according to the present invention are usefully used in solvents, adhesives, resins, inorganic intermediates, lubricants, surfactants and the like.

Claims (8)

Compound represented by the formula (I), (A) nickel in an amount corresponding to 10 to 70 weight percent of the metal nickel, and (B) oxides of silicon, aluminum, magnesium, titanium and zirconium; And reacting at least one of these oxides with hydrogen in the presence of a solid catalyst consisting of at least one compound selected from the group consisting of synthetic or natural inorganic oxides having their structural units, thereby preparing ether compounds of formula (II) or (III) How to: Formula I (Wherein R ¹ and R ² are each an alkyl group or a cycloalkyl group, which may be the same or different, in many repeat units R ¹ may be the same or different and n is an integer from 1 to 50) Formula II Formula III Wherein R ¹ , R ² and n are each as defined in formula (I) above) The method of claim 1, Solid catalyst (A) nickel in an amount corresponding to 10 to 70 weight percent of the metal nickel, and (B) at least one oxide selected from silica, alumina, silica-alumina, magnesia, silica-magnesia, titania, zirconia, zeolite, activated clay and diatomaceous earth Process for the preparation of ether compounds. The method of claim 1, The solid catalyst is selected from the group consisting of nickel-silica-alumina catalyst, nickel-alumina catalyst, nickel-silica-alumina-magnesia catalyst, nickel-zirconia catalyst and nickel-diatomaceous earth catalyst Process for the preparation of ether compounds. The method of claim 1, The reaction of the acetal compound with hydrogen is carried out at a temperature of 70 to 200 ℃ Process for the preparation of ether compounds. The method of claim 1, The reaction of the acetal compound with hydrogen is carried out under a pressure of 3 to 60 kg / cm 2 Process for the preparation of ether compounds. The method of claim 1, Acetal compound is continuously reacted with hydrogen in a fixed phase manner Process for the preparation of ether compounds. The method of claim 1, Filling the solid catalysts in the fixed bed reactor and of the acetal compound from 0.01 to 10h ^-1 LHSV [[capacity threshold, space velocity; (Raw material feed rate, ml / hr) / (catalyst amount, ml)] was continuously fed into the catalyst bed and reacted with hydrogen to continuously produce ether compounds. Process for the preparation of ether compounds. The method of claim 1, The acetal compound is reacted with hydrogen in the presence of a solid catalyst in a suspended state to produce an ether compound. Process for the preparation of ether compounds.